N-(5-chloro-tert.butyl-2-thiadiazolyl)carboxamides and use to combat unwanted vegetation

ABSTRACT

NEW N-(CHLORO-TERT,BUTYLTHIADIAZOLYL) AMIDES ARE EMPOLYED TO COMBAT UNDESIRED VEGETATION BOTH PRE-EMERGENTLY AND POST-EMERGENTLY. CYCLOPROPANECARBOXAMIDES ARE PREFFERED.

United States Patent Ofice N-(5-CI-ILORO-TERT.BUTYL 2 THIADIAZOLYL) Int. Cl. A01n 9/12 US. CI. 71-90 2 Claims ABSTRACT OF THE DISCLOSURE New N-(chloro-tert.butylthiadiazolyl) amides are employed to combat undesired vegetation both pro-emergently and post-emergently. Cyclopropanecarboxamides are preferred.

DESCRIPTION OF THE INVENTION CH3 S x-om-b- I v R o in which X represents hydrogen or a chloro substituent, R is hydrogen or a methyl or ethyl substituent and -R is selected from methyl, chloromethyl, ethyl, propyl, isopropyl, cyclopropyl, chloropropyl, and methoxymethyl substituents, preferably cyclopropyl. The novel compounds may be prepared from available starting materials according to procedures of the type specifically exemplified below.

Preparation of 2-amino-5-(fl-chloro-u,a-dimethylethyl)- 1,3,4-thiadiazole To a well stirred suspension of 150 g. of thiocemicarb- 3,823,005 Patented July 9, 1974 addition was complete, heating was continued until HCI evolution ceased. After cooling, the supernatant liquid was decanted from the solid mass and 500 ml. of water was added. With cooling, sodium hydroxide pellets were added until a pH of 10 was maintained. The resulting precipitate was collected, washed with water and air dried to give 266 g., m.p. 174-176 (85%). Recrystallization from methanol gave the analytical sample, mp. 176-177".

Anal. Calcd. for CgH ClN S: C, 37.60; H, 5.26; N, 21.92.

Found: C, 37.67; H, 5.47; N, 22.20.

Preparation of 2-methylamino-5-a,a-bis-chloromethyl-; ethyl)-1,3,4-thiadiazole To a stirred suspension of 34 g. of 4-methylthiosemicarbazide in 150 ml. of dioxane was added g. of bis- (2,2-chloromethyl)propionyl chloride, then heated to reflux temperature. Carefully, 50 g. of phosphorus oxychloride was added and heating continued until H=Cl evolution ceased. After cooling, the supernatant liquid was decanted from the viscous material that had separated, water was added and the mixture taken to a pH of 10 with sodium hydroxide pellets. No precipitate formed. The solution was extracted with CHClwhich was shaken with water, saturated sodium chloride and dried over Na SO The CHCl was removed at reduced pressure and the residue crystallized with a mixture of CH Cl -petroleum ether to give 27.8 g., mp. 105-107 (36% An analytical sample, mp. 108-109, was prepared from CH -Cl petroleum ether.

Anal. Calcd. for C H Cl N S: C, 35.01; H, 4.62; N,

17.50. Found: C, 35.31; H, 4.80; N, 17.66.

Preparation of 2-isobutyrylamido-5-(,9-ch1oro-a,udimethylethyl) -1, 3,4-thiadiazole To 6.0 g. of 2-amino-5-(B-chloro-a,zit-dimethylethyl)- 1,3,4-thiadiazole in 25 ml. of pyridine, was added 6.0 g. of isobutyryl chloride at room temperature. The reaction was allowed to stir for 3 hours, then was poured into ice water. The resulting solid was collected, washed with water and air dried to give 6.5 g. mp. 129-131 (81%). An analytical sample was prepared from CH C'l petroleum ether, mp. 132-133".

Anal. Calcd. for C H ClN -OS: C, 45.88; H, 6.16; N,

16.05. Found: C, 46.14; H, 6.20; N, 16.23.

TABLE 1 1 ,s -CH-,-C Trlq-lo-n' Calcd. Found M.P.,

x R R o. o H N o H N H H Cyclopropyl 137-138 46.24 5.43 16.18 46.03 5.43 16.03 H H omens 132-133 45.88 6.16 16.05 45.14 6.20 16.23 H H 0H40H40H. 134-136 45.88 6.16 16.05 45.06 6.04 16.21 121 H o 3 214-215 41.11 5.17 17.98 40.90 5.11 17.76 H H 0116501. 116-118 40.55 5.10 1418 40.38 5.06 13.97 H H -OH4C-CH9 9091 40.99 5.35 15.93 41.02 5.36 15.72 121 on, omoHm 112113 47.90 6.58 15.23 47.89 6.59 15.16 H on, 0 0H04 104-105 49.73 6.95 14.50 49.51 6.99 1437 H CH9 H201 84-85 38.31 4.64 14.89 38.31 4.70 1493 E 011403, Cyelopropyl 82-83 50.08 6.30 14.60 50.13 6.39 1470 01 H 0 761 116 11 156157 40.83 4.45 14. 26 40.86 4.39 14.07 01 H cm H04 176-177 40.55 5.10 14.18 40.80 5.06 14.18 01 H 011.0151. 145-146 38.31 4.64 14.89 38.39 481 14.57 01 CH;- Cyolopropyl 104-105 42.86 4.90 13.63 43.04 5.02 13.80 01 0H, CH3 120-121 38.31 464 14.89 38.29 4.75 14.93 e1 0115 01140116 100-101 40.55 5.10 14.18 40.56 5.22 14.23 01 onion, Cyolopropyl 101-102 44.73 5.32 13.04 4486 5.22 13.18 (11 0114011. 11.0114 139-140 42.59 5.52 18.54 42.68 5.50 13.55

azide and 225 g. of fi-chloropivolic acid in 500 ml. of dioxane heated at reflux temperature was added 262 g. of phosphorus oxychloride over a 1 hr. period. When the Combating Unwanted Vegetation I 63m I A5593 55 33 $5: a}: 3; in: in; in: umomu an umOM wu m amo m mum 6 6 6 z z z z z z 3 5 31 i E i mo Eo o z o mo 6 m o o Eo mo mo o o fio m w m w mo E0 E0 E0 N 62 uESnEo 2% 5 B2B .595 5 26% 3 2 38 M5 3 253 2a 8 @5 33 68 96B 33 cda m0 3 0% 58 5%? no :69:00 3:8 .5 0 Q3 5 3388 $3 269:8 5 625w uuntumuu 83630.5 05 2 52 .6358 m 5 no 250 m .556 a 5 02:56 5333 2: n55: uanomfiou 05 mm E552: 5 0 0 08 05 8 5 68a c238? 2523: 388 E 3: How 0 0 .33 uobumua 2 WQ mQ M H F "m0 m% m O N EH m w w m .mw% E6 E6 6 w m IHWMM EEEOEO E5 6 w w w w HHHH I IWMMMM E6 "M0 6 w I I m HHmmM so 0 6 w v w w hmwmw gnoas o mo 6 IIQHW W m w w 8 m 6 "mo wo I v m Q N m .I N w w I. i m mo m 6 I- w w w Q w I IMM% 30 m 6 HHHHHHHHHHM IIIIIIIIIIIIIIIIIIIIIIIIIIII II M m w w IIIIH IIIIII H I IWMMMM 3. 2 0 "m0 Hm HHHHHHHHHH IIIIIII IIWIIIIIIIIIIIIII.HHHH IIIIII Q w w. IIIIIIIIIIIIIII HMMMW HO MO M0 2 N I N n a l a II d a H :66 mo m 7 We claim: a compound having the structural formula 1. Combating unwanted vegetation by applying to the CH3 locus of the vegetation a herbicidally effective amount of of a compound having the structural formula CI CH"'$ T f f cm 8 /Cl& References Cited GHQ-43% TIf-(fi-CH-CH: UNITED STATES PATENTS t i i H 0 10 3,429,688 2/1969 Duerr et al 71-90 NN 3,306,727 2/1967 Neighbors 71-90 JAMES 0. THOMAS, JR., Primary Examiner 2. Combating unwanted vegetation by applying to the locus of the vegetation a herbicidally effective amount of 260 306'8 D column 1, ine 27, the'word thiocex'nicjdrb-"Y sh ou ld 22253?" I ;UNITED STATES PATENT OFFiIjC-fE [CERTIFICATE OF CORRECTION PatentNo. 3,823,005 v Dated. uly 1914 ,lnvencoz-(s) William C. Doyle; Jr'. and Joel L Kirkpatrick It is certified thatierror appears in the aboveidehtified patent and thet said Letters Patent are hereby correted vas shown be 1pw:

- Table 1-, line 5, under the heading "R" (c-fij -yscl." should read 5- 2) 1 I and sealed this 3rd dey 10f De ee xhber 1974 v EAL) Atte s t:

"M coy- M." GIIBSYON JR. e c, MARSHALL'DAN'N 1 7 U Attesting fQfficer, cbmissioneg of Patents I 

